Near‐IR Absorbing Ruthenium Complexes of Non‐Innocent 6,12‐Di(pyridin‐2‐yl)indolo[3,2‐b]carbazole: Variation as a Function of Co‐Ligands

This article deals with the hitherto unexplored metal complexes of deprotonated 6,12‐di(pyridin‐2‐yl)‐5,11‐dihydroindolo[3,2‐b]carbazole (H₂L). The synthesis and structural, optical, electrochemical characterization of dimeric [{Ru^III(acac)₂}₂(μ‐L^.?)]ClO₄ ([ 1 ]ClO₄, S=1/2), [{Ru^II(bpy)₂}₂(μ‐L^.?)](ClO₄)₃ ([ 2 ](ClO₄)₃, S=1/2), [{Ru^II(pap)₂}₂(μ‐L^2?)](ClO₄)₂ ([ 4 ](ClO₄)₂, S=0), and monomeric [(bpy)₂Ru^II(HL^?)]ClO₄ ([ 3 ]ClO₄, S=0), [(pap)₂Ru^II(HL^?)]ClO₄ ([ 5 ]ClO₄, S=0) (acac=σ‐donating acetylacetonate, bpy=moderately π‐accepting 2,2’‐bipyridine, pap=strongly π‐accepting 2‐phenylazopyridine) are reported. The radical and dianionic states of deprotonated L in isolated dimeric 1 ⁺/ 2 ³⁺ and 4 ²⁺, respectively, could be attributed to the varying electronic features of the ancillary (acac, bpy, and pap) ligands, as was reflected in their redox potentials. Perturbation of the energy level of the deprotonated L or HL upon coordination with {Ru(acac)₂}, {Ru(bpy)₂}, or {Ru(pap)₂} led to the smaller energy gap in the frontier molecular orbitals (FMO), resulting in bathochromically shifted NIR absorption bands (800–2000 nm) in the accessible redox states of the complexes, which varied to some extent as a function of the ancillary ligands. Spectroelectrochemical (UV/Vis/NIR, EPR) studies along with DFT/TD‐DFT calculations revealed (i) involvement of deprotonated L or HL in the oxidation processes owing to its redox non‐innocent potential and (ii) metal (Ru^III/Ru^II) or bpy/pap dominated reduction processes in 1 ⁺ or 2 ²⁺/ 3 ⁺/ 4 ²⁺/ 5 ⁺, respectively.     

Squeezed Atom Laser for Bose-Einstein Condensate with Minimal Length

We study a protocol for constructing a squeezed atom laser for a model originating from the generalized uncertainty principle. We show that the squeezing effects arising from such systems do not require any squeezed light as an input, but the squeezing appears automatically because of the structure of the model it owns. The output atom laser beam becomes squeezed due to the nonlinear interaction between the Bose-Einstein condensate and the deformed radiation field created due to the noncommutative structure. We analyze several standard squeezing techniques based on the analytical expressions followed by a numerical analysis for further insights.

     

Controlling decoherence via PT-symmetric non-Hermitian open quantum systems

We have studied the effect of a non-Hermitian Bosonic bath on the dynamics of a two-level spin system. The non-Hermitian Hamiltonian of the bath is chosen such that it converges to the harmonic oscillator Hamiltonian when the non-Hermiticity is switched off. We calculate the dynamics of the spin system and found that the non-Hermiticity can have positive as well as negative effects on the coherence of the system. However, the decoherence can be completely eliminated by choosing the non-Hermiticity parameter and the phase of the system bath interaction appropriately. We have also studied the effect of this bath on the entanglement of a two-spin system when the bath is acting only on one spin.     

Reactivity of triazolyl Schiff bases with Ru(II)-2,2′-bipyridyl: Synthesis,spectroscopic characterization of isomers and their photo-physical properties

The condensation of 3-amino-1H-1,2,4-triazole with benzaldehyde and terephthalaldehyde provides the bidentate and tetradentate Schiff bases 1,2,4-triazolo-3-imino-benzene L¹H and 1,4-bis(1,2,4-triazolo-3-imino)benzene L²H₂, respectively. The well characterized Schiff bases were allowed to react with cis-Ru(bpy)₂Cl₂ · 2H₂O. Isomers of the mononuclear complexes Ru(bpy)₂L¹]PF₆ · NH₄PF₆ (1a, N4) and [Ru(bpy)₂L¹]PF₆ · 0.5NH₄PF₆ (1b, N2), and the dinuclear Ru(II) complexes [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₂ · NH₄PF₆ (2a, N4N4), [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₂ · NH₄PF₆ · 2H₂O (2b, N2N2) and [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₃ · NH₄PF₆ (2c, Ru(II)-Ru(III)) were separated by column chromatography and characterized by their elemental analysis, FAB mass and spectral (IR, NMR, UV–Vis) data. The data obtained suggest that the ligands are bound to the metal centre via the N4 and N2 atoms of the triazole moiety along with the N (imine) atom. The complexes display metal-to-ligand charge-transfer (MLCT) transitions in the visible region from the dπ(Ru^II) → π^∗L transition. Highly intense ligand-based π→π^∗ transitions are observed in the UV region. A dual emission occurs from the N2 and N2N2 isomers.     

Self-assembly of a luminescent zinc(II) complex: a supramolecular host-guest fluorescence signaling system for selective nitrobenzene inclusion

A luminescent Zn(II) complex, [Zn(bpy)(aba)2] (1) {bpy = 2,2'-bipyridyl and aba = 4-dimethylaminobenzoate} has been synthesized as a white solid. Complex 1 shows unusually high selectivity toward nitrobenzene in the presence of other organic guests in solution, as well as in the vapor phase, resulting in both a dramatic color change and a concomitant quenching of luminescence. When crystallized from nitrobenzene, 1 affords deep red crystals with the composition [Zn(bpy)(aba)2] x C6H5NO2 (2) as a hydrogen-bonded channel structure via unusual intermolecular C-H...C(sp3) and H...H interactions. Inside the channels, nitrobenzene molecules form infinite polar linear tapes through strong C-H...O interactions in a head-to-tail fashion. The desorption and resorption of nitrobenzene can be achieved in a thermally reversible manner that can be monitored by X-ray powder diffraction patterns.     

Experimental observation of dust circulation in unmagnetized cogenerated dusty plasma

The vortex motion of a dust cloud was experimentally observed in unmagnetized cogenerated dusty plasma in different experimental parameters. Particle image velocimetry analysis demonstrated that several vortex zones exist in the dust cloud at relatively low pressures (0.06 mbar (or 6 Pa)–0.08 mbar (or 8 Pa)) and low discharge voltages (peak‐to‐peak voltage 540–560 V), whereas in relatively high pressure (0.4 mbar (or 40 Pa)–0.7 mbar (or 70 Pa)) and high discharge voltage (peak‐to‐peak voltage 690–740 V), dust vortices formed in dense dust cloud with background plasma fluctuation.     

Antitumour effect of Diospyros cordifolia bark on Ehrlich ascites carcinoma-bearing Swiss albino mice

Diospyros cordifolia Roxb. (Ebenaceae), commonly known as Indian ebony, is used traditionally for several medicinal purposes. In this study, the methanol extract of D. cordifolia bark (MEDC) was evaluated for its antitumour effect against Ehrlich ascites carcinoma (EAC)-bearing Swiss albino mice. Twenty-four hours after intraperitoneal inoculation of tumour (EAC) cells in mice, MEDC was administered intraperitoneally at 25 and 50?mg kg?1 bodyweight for 9 consecutive days. On the 10th day, half of the mice were sacrificed to determine the tumour volume, viable and non-viable tumour cell counts, and rest were kept alive for the assessment of median survival time and increase in life span. Haematological profiles were also determined. MEDC exhibited a marked decrease in tumour growth parameters and increased the survival rate of EAC-bearing animals. MEDC normalised the haematological parameters as compared with the EAC control mice. Therefore, this study demonstrated that D. cordifolia bark possessed remarkable antitumour efficacy.     

Protein-mediated efficient synergistic "antenna effect" in a ternary system in d(2)o medium

A ternary system consisting of a protein, catechin (either + or - epimer), and Tb(III) in suitable aqueous buffer medium at physiological pH (= 6.8) has been shown to exhibit highly efficient "antenna effect". Steady state and time-resolved emission studies of each component in the binary complexes (protein with Tb(III) and (+)- or (-)-catechin with Tb(III)) and the ternary systems along with the molecular docking studies reveal that the efficient sensitization could be ascribed to the effective shielding of microenvironment of Tb(III) from O-H oscillator and increased Tb-C (+/-) interaction in the ternary systems in aqueous medium. The ternary system exhibits protein-mediated efficient antenna effect in D(2)O medium due to synergistic ET from both the lowest ππ* triplet state of Trp residue in protein and that of catechin apart from protection of the Tb(III) environment from matrix vibration. The simple system consisting of (+)- or (-)-catechin and Tb(III) in D(2)O buffer at pH 6.8 has been prescribed to be a useful biosensor.     

Theory of Jovian Kilometric Radiation

This report presents a theoretical model of extraordinary mode radiation in presence of low frequency whistler mode. We show that the generation mechanism of extraordinary mode emission in the presence of whistler mode is based on the plasma maser theory. Application of theoretical results to Jovian Kilometric radiation is examined.